Lithium and lithium ion batteries (collectively referred to herein as “lithium battery”, “LIB” and grammatical variations thereof) are playing an increasingly important role as power sources for electronic devices and electric vehicles. Development of LIBs with higher energy and/or power densities than the current generation of batteries is an active field of research. Such “high voltage” batteries can be made smaller and lighter than the current standard, which is extremely desirable, e.g., for vehicular uses and for personal electronic devices. Cell energy is governed by the equation Ecell=Q×(V−i R), where Q is capacity, V is voltage, i is current and R is resistance. High energy cathodes comprising various transition metal oxide materials have been identified, which need to be cycled at high voltages (greater than about 4.5 V) to achieve suitably high energy densities. Examples of such materials include, e.g., lithium nickel/manganese/cobalt oxide-graphite cells such as Li1.2Ni0.15Mn0.55Co0.1O2 / carbon (cathode)-graphite (anode) cells. Unfortunately, high voltage cycling can lead to increases in electrolyte oxidation and acceleration of transition metal oxide dissolution. Stable solid electrolyte interface (SEI) passivation layers at the positive and negative electrodes can ameliorate some of these undesirable effects. Consequently, there is an ongoing need for electrolyte compositions that promote stable SEI formation in high voltage LIB applications. The electrolyte compositions described herein address this ongoing need.